Organic phosphorus compounds



3,014,955 ORGANIC PHOSPHORUS COMPGUNDS Ernst Beriger, Allschwil,.ilwitzerland, assignor to Cilia Limited, Basel, Switzerland N Drawing.Filed June 22, 1959, Ser. No. 821,696 Claims priority, applicationSwitzerland July 10, 1958 11 Claims. (Cl. 269-461) This inventionprovides organic phosphorus compounds of the general formula in which Rand R each represent an alkyl, cycloalkyl, aralkyl, aryl or heterocyclicradical which may be substituted or R and R together form part of a ringsystem, R represents a branched or unbranched alkyl radical interruptedby at least one oxygen or sulfur atom, preferably by at least two oxygenor sulfur atoms, or represents an alkyl-aryl radical, R represents ahydrogen or halogen atom or an alkyl radical, R represents an aliphatic,alicyclic, aromatic or heterocyclic radical, X and Y each represent O,S, NH or and Z represents an oxygen or sulfur atom, and n and m eachrepresent the whole number 1 or 2.

The above Formula 1 comprises any possible stereoisomers, particularlythe cisand corresponding transisomers.

The compounds of the above formula are new and are valuable agents forcombating pests, especially insects and aearids. They are activeagainstvarious stages of development, such as eggs, larvae and imagines, andthey are effective as contact poisons and stomach poisons. Suitablesubstitution products are distinguished by rapid hydrolyticdecomposition in the air and by their relatively low toxicity towardswarm-blooded animals, so that they can be used for combating pests incrops shortly before they are harvested. Especially valuable asinsecticides are compounds of the general formula or of the formula inwhich m, m, n and n each represent a whole number from 1 to 4, p, q andq a whole number from 1 to 10,

3,914,955 Patented es. 2%, 1981 p being preferably at least 2, and Zrepresents an oxygen or sulfur atom, R represents a hydrogen or chlorineatom, and R represents a lower alkyl group, especially a methyl group,or a phenyl group which may be substituted. Among these compounds thoseof the formula or of the formula in which R, R n, m, X, Y and Z have themeanings given above, and R represents an alkyl group contain- CH20-ACH3 H O CHzO-A.

ing 1-4 carbon atoms, is condensed with a compound of the formula Hal inwhich R R and K, have the meanings given above, and Hal represents ahalogen atom, such as bromide or preferably chlorine, accompanied by thesplitting oil of a compound of the formula R Hal.

The new compounds can also be obtained by reacting a compound of theformula in which R, R 71, m, X, Y and Z have the meanings given above,and Me represents an alkali metal, such as sodium, with a compound ofthe formula O=(l)--R4 Ha1O-R,

in which R R R and Hal have the meanings given above. The compounds inwhich R represents a hydrogen atom or alkyl group can also be made bythe following condensation:

used as starting materials are derivatives of trivalent phosphorus,whereas the compounds of the invention are derivatives of pentavalentphosphorus.

Among the compounds of the above formula those are most easilyobtainable in which the symbols X, Y and Z represent oxygen atoms. Theycorrespond to the formula P-ORs Er -O and can be made by methods inthemselves known.

The aliphatic radicals which the symbols R and R may represent, may havestraight or branched chains and be saturated or unsaturated, and theymay be substituted or unsubstituted. There may be mentioned, forexample, the following groups: Methyl, ethyl, propyl, isopropyl, butyl,hexyl, Z-ethylbutyl, octyl, Z-butyloctyl, dodecyl, octadecyl, allyl,2-chlorethyl; and also radicals containing thiocyano, cyano or estergroups. The radicals R and R may be identical or diiferent from oneanother. R is advantageously a low molecular alkyl group having 1 to 4carbon atoms. There may be mentioned, for example, the followingcompounds: Trimethylphosphite, triethylphosphite, tripropylphosphite,diethyl dodecylphosphite, tri-(Z-chloroethyl)-phosphite or the ester ofthe formula The aromatic radicals which R and R may represent, may bemononuclear or polynuclear and may contain nuclear substituents. Theremay be mentioned the phenyl, 2- or '4-chlorophenyl, 2:4-dichlorophenyl,4-methoxyphenyl, 4-nitrophenyl, naphthyl and 4-diphenyl groups. Theremay be mentioned compounds, such as 2:4-dichlorophenyldiethyl phosphiteand 4-chlorophenyldimethyl phosphite. There may also be mentionedcompounds in which one or two radicals are bound directly through acarbon atom to the phosphorus atom, for example, phenyl-phosphinic aciddiethyl ester of the formula PQC2H5 CzHsO Among the araliphatic radicalswhich R and R may represent, there may be mentioned the benzyl group;

among cycloaliphatic radicals the cyclohexyl group; and amongheterocyclic radicals the tetrahydrofurfuryl group. Starting materialscontaining such radicals are, for example, cyclohexyl diethyl phosphite,tetrahydrofurturyl dimethyl phosphite and dibenzylpropyl phosphite.Among the compounds in which X and Y represent sulfur atoms there may bementioned triethyl thiophosphite of the formula CaHsS P-sCzH,

C2H5S and among those in which X and Y represent nitrogen there may bementioned the compound of the formula zHmN P-O (12H;

z m The compounds of the general formula are phosphoric acidmonohalides, for example, phosphoric acid diethyl ester monochloride,thiophosphorie acid diethyl ester monochloride andbis-dimethylamido-phosphoric acid monochloride.

The compounds of the general formula l rt-K 0 Hal 0R2 are esters ofhalogenated acyl-acetic acids derived from aliphatic, alicyclic,aromatic or heterocyclic carboxylic acids, and advantageously aceto-,benzoyl-, hexahydrobenzoyl-, furoylor tetrahydrofuroyl-acetic acid, withmonoalkyl ethers of monoaryl ethers of dihydric aliphatic alcohols orthe corresponding thio-ethers. The radical R may be a branched orunbranched alkyl or alkyl-aryl radical interrupted by at least one etheroxygen bridge or by a sulfide bridge, preferably by at least two etheroxygen bridges or sulfide bridges, and may correspond more 1 especiallyto the formula in which m, in, n and n represent whole numbers from 1 to4, p, q and q represent a whole number from i to 10, I being preferablyat least 2, and Z, represents an'oxygen or sulfur atom. There maybementioned for example a lower alkoxyalkyl group such as themethoxyethyl, ethoxyethyl, propoxyethyl, or butoxyethyl group, or aphenoxyalkyl group such as the phenoxyethyl group; and particularlypolyalkylene-glycol monoalkyl other groups, such as the diethyleneglycol monomethyl ether radical, the diethylene glycol monoethyl etherradical, the diethylene glycol monopropyl ether radical and themonoethylene glycol monomethyl ether radical, or glycerine-dialkyl othergroups, such as the glycerine-lz3- dimethyl ether radical. The radical Rmay represent a halogen atom, advantageously a chlorine atom, or ahydrogen atom or an alkyl group preferably containing 1 to 4 carbonatoms, such as the methyl group. R may represent a heterocyclic radical,such as the furfuryl or tetrahydrofurfuryl group, or an aryl radical,for example, the phenyl, chlorophenyl or nitrophenyl radical, or acycloalkyl radical such as the cyclohexyl group, or an alkyl group suchas the methyl or ethyl group. Among reaction components of the formulalast mentioned above there may be mentioned: ot-Chloracetoaceticacid-Z-methoxyethyl ester, ct-chloracetoacetic acid 2-phenoxyethylester, aza-dichloracetoacetic acid-Z-ethoxyethyl ester,am-dichloracetoacetic acid-Z-phenoxyethyl ester,a:a-dichlorobenzoylacetic acid-Z-ethoxyethyl ester, 0210cdichlorobenzoylacetic acid-Z-methoxyethyl ester, a:a-dichloro-4-chlorobenzoylaceticacid-Z-ethoxyethyl ester, occhloro-4-nitrobenzoyl-aceticacid-Z-ethoxyethyl ester, azudichlorofuroyl-acetic acid-2-ethoxyethylester and madichlorohexahydrobenzoyl acetic acid-Z-ethoxyethyl ester.

For making the compounds of the invention the reaction components areheated at a raised temperature, for example, within the range of 50200C. and advantageously about 90 C. to 150 C. It may be of advantage orconvenient to Work in an inert solvent, such as benzene, toluene,xylene, chlorobenzene, and, if desired, in an atmosphere of an inertgas, for example, nitrogen, and/ or under reduced pressure.

As stated above the compounds of this invention are valuablepest-combating agents, and especially insecticides and acaricides.

Accordingly, the present invention provides also pest combatingpreparations containing the new products as active principle, as Well asa method of combating pests with such preparations. Advantageously,there are used compounds of the general formula in which R stands for aradical of the formula l C m+1 Zm+2 Z O nHzmu L .In or of the formula inwhich m, m, n and n stand for small whole numbers from 1 to 4, p, q andq for whole numbers from 1 to 10, p being preferably at least 2, and Zstands for oxygen or sulfur, R for a hydrogen atom or a chlorine atomand R for an alkyl radical of low molecular Weight or a phenyl radicalwhich may be substituted.

A wide variety of bodies can be protected against pests or harmfulinsects and acarids with the use of a preparation in which the supportfor the active principle may be a gaseous, liquid or solid substance. Asbodies to be protected, or used as supports, may be mentioned, forexample, air, more especially in rooms; liquids, such as water in ponds,and finally any dead or living solid substratum, such as any kind ofobject in lived-in rooms, in cellars, in lofts, in stables; furthermorefurs, feathers, wool or the like; as Well as living plants or animals intheir different stages of development, provided that they are immune tothe pest combating agents.

The combating of the pests is carried out by the usual methods, forexample by treating the body to be protected with the compound in vapourform, for example as fumigants or in the form of dusting or sprayingpreparations, for example as solutions or suspensions prepared withwater or with a suitable organic solvent such, for example, as alcohol,petroleum, tar distillates or the like. It is also possible to useaqueous solutions or aqueous emulsions of organic solvents containingthe active principle for brushing, spraying or dipping the object to beprotected.

The spraying and dusting preparations may contain the conventional inertfillers or identifying agents such as caolin, gypsum or bentonite orfurther additives or the like; they may also contain the usual Wettingagents and adhesives to improve the wetting properties and the adhesion.The pest combating preparations may be manufactured in powder form or inthe form of aqueous dispersions or pastes or of self-dispersing oils.

The pest combating preparation may contain a compound of the inventionas the sole active principle or in combination with other insecticidesand/or fungicides. Such preparations are used for plant protectionaccordingto the usual spraying, casting, dusting and fumigating methods.

Parts in the following examples are by Weight, and the relationshipbetween parts by weight and parts by volume is the same as that betweenthe kilogram and the liter.

Example 1 A mixture of 12.15 parts of aza-dichloroacetoaceticacid-Z-ethoxy ethyl ester and 15 parts of chlorobenzene is heated to 140C. In the course of 5 minutes 6.8 parts of trimethyl phosphite are addeddropwise to the mixture. The reaction is completed by refluxing for ashort period. 2.25 parts of methyl chloride have collected in areceptacle. The solvent and readily volatile constituents are removed ina water-jet vacuum at C. bath temperature, to yield 16.05 parts of anoily liquid which can be distilled in a high vacuum and boils at136-140" C. under a pressure of 0.02 mm. Hg.

The analysis of the condensation product obtained in this mannercorresponds to the empirical formula C H O CIP.

Calculated: Cl, 11.20; P, 9.78%.

Found: Cl, 11.24; P, 9.76%.

Example 2 9.1 parts of triethyl phosphite are added dropwise tomaintained at the boil for another hour, by which time 2.8 parts ofethyl chloride have collected in a cooled receptacle. The solvent andthe readily volatile constituents are removed in a Water-jet vacuum at95 C. bath temperature, to yield 17.7 parts of the condensation productof the empirical formula C H O ClP, boiling at 146-150 C. under 0.015mm. Hg pressure.

Example 3 15.25 parts of aza-dichlorobenzoylacetic acid-Z-ethoxy ethylester in 15 parts of chlorobenzene are heated to the boil and treateddropwise with 6.8 parts of trimethyl phosphite. When all has been added,the bath is maintained at 150160 C. for 1 hour longer, by which time 2.4parts of methyl chloride have collected in a cooled recep which time 3.4parts of methyl chloride have collected in a cooled receptacle. Themixture is freed from the readily volatile constituents in a water-jetvacuum at 95 C. bath temperature, and the residue is distilled in a hightacle. The mixture is freed from the readily volatile 5 vacuum; theproduct boils at 124-128" C. under 0.02 mm. constituents in a water-jetvacuum at a bath temperature Hg pressure. of 95 C., to yield as residue180 parts of a heavy oil Exam le 6 which can be mixed with alcohol oracetone in any prop Port-Ion E l 4 14.05 parts of triethyl phosphite areadded dropwise to P 10 a. boiling mixture of parts ofot-chloroacetoacetic acid- 15 .25 parts of aza-dichlorobenzoylaceticacid-Z-ethoxy Z-methOXY ethyl ester and Parts y Volume 0f chloroethylester in 15 parts of chlorobenzene are treated with h After 'P addltlhhis complete the 9.1 parts of triethyl phosphite as described in Example3, ihhmlfe 1S P bolllhg 1 hour longer, after Which whereby 3 parts ofethyl hl id are split ff, Th time 3.6 parts of ethyl chloride havecollected in a cooled reaction mixture is evaporated in a water-jetvacuum to 15 p' The h and the readily Volatile constiyield 20.1 parts ofa heavy oil which is readily soluble thehts 3T6 removhd 111 'l Vacuum atbath in isopropanol and in acetone temperature, and the residue isdistilled in a high vacuum. E l 5 The product (18.3 parts) boils at133-135 C. under 0.04

xamp 8 mm. Hg pressure. I 15 parts of a-chloroacetoacetic acid-Z-methoxyethyl 20 The acetoacetic acid esters halogenated in the a-posiester in20 parts by volume of chlorobenzene are heated tion, listed in thefollowing table, can be reacted in an to 140 C. and treated dropwisewith 10.5 parts of trianalogous manner with tertiary phosphites. Theresultmethyl phosphite. When the dropwise addition is coming phosphoricacid esters are characterized by their plete the bath is maintained at135-140" C. for 1 hour, by boiling points.

Degree of Boiling halogenation of No. Acetoaeetic acid ester the aeeto-Phos- Phosp oric acid ester acetic phite at C. under acid mm. ester inHg (I-pOSitiOH u 6 1--.- CHaOOCHaCOOCZHLOCHI dicgo- (omo P (GHtOhP-O 0:0147448 0.04

l 8, Iii-P. 73 0. under 0.01 mm. Hg. COOCaHtO OH:

[1 E 2- OHQGOOHQCOOCZHQOCH! do (C2H50)IP (CtH5O)aP-0O=0 -140 0.03

IB.P. 73 0.1mder 0.01 mm. Hg. 0 00 621140 OH;

( OH: /H 3 CHQCOGHQCOOC2H4OC2HB molllllo- (CHaOkP (OHsO)2P-" C 130 0. 05

0 O- B.P. 86 C. under 0.03 mm. Hg. ride. 0 O OCgHiO 01H;

[1 (13Ha 4--.. OH3COCH2GO0C2H4OG2HB .-do--- (021550? (C2H5O)2P' O 0 8132 0. 035

18.1. 86 C. under 0.03 mm. Hg. 00 OC2H40 02115 11 (I333 5--.-CH1COCHQCOOC2HQOCKH7(D) -do (CHsO)aP (CHaO)nP-OC=C 13 -133 M4 3.1. 86-89C. under 0.04 mm. Hg. 0 00 o=Ht0o3H1(n) r H 6---- OHEGOCHQCOOCQHQOCQIKD)..do (C2H50)3P (OtHs0)a 00=C 132434 0.02

13.1. s0-s9 C. under 0.04 mm. Hg. 7 0 00041140 0311101) n i 7----oHtoooHtcoootHto 0311101) diclzilo- (CHaO)aO (CH30 2PO 0:0 152-154 0.1

['1 e. B.P. 86-89 C. under 0.04 mm. Hg. COOOtHtO 0311701) 7 H (3H3 C1s-- CH3COCHQCOOCzH4OC3H7 H -do.- (0211mm (CzH5O)2P-OC=C 148 0,02

13.1.06-89 0. under 0.04 mm. Hg. oooctrno (1311101 11 R 9.--.CHSCOCHiCOOOZHAOC-iHD mglito- (01130? (CH20)2POC=C 139-140 0.03

0 OP B.P. 93-94" 0. under 0.03 mm. Hg. ride. 0 0 0 021140 04H 11 E 10---CHBCOCH2QOOClH4O 04H!) -do (071150)? (Gamma-00:0 144-147 0.02

13.1. 93-94 0. under 0.03 mm. Hg. 0 0 0 0111.0 04H,

I 11 u 11--- CH3CO0H2COOC2HOC4HQ dlchdlo- (CH30)3P (CHaOhP-o C=0\154-155 0.00

' 1'1 6. Bl. 93-94" 0. under 003 mm. Hg. 3 1 COO 0111 004119 Degree ofBoiling halogen- No. Acetoacetic acid ester t c e ig- Phos- Phosphoricacid ester aggiic phite at C. urfligner ester in Hg aposition CH: Cl42... CHaCOCHaCOOCflLOCHzQ dighilgj (CH3O)3P (CH O)a1 O 3=O B.P. 1aa-1ss0. under 0.02 mm. Hg. 0 O CZHO Q non-distillable oil, readily soluble inacetone and l-propanol. CHQO CH3 CH H 43-.- CHaOOCHzCOOCI-I mgfifi;(CHaOhP (CH;O) i -O( J=C CH O CH 127-134 0.01

CHzOCHa ride. COOCH B.P. 91-94" C. under 0.01 mm. Hg. CH2O CH:

CHQO CH: CH3 H 44..- CH3COCH2COOCH .-.do----- (C2H50)3P (GzHO) 1 O C=OCHzO OHa 134438 0.01

CH2O CH: OOOC Bl. fill-94 C. under 0.01 mm. Hg. CHgO CH5 CHzOCHo C Ha Cl45.-- CHaCOCHzCOOCH dilcihgg: (OHaOM (OHs0)1O '3=C CHIOCHa lss-iso 0.15

01120 CH3 0 O O CH B.P. 91-94 0. under 0.01 mm. Hg. CHzO CH3 CHrOCHs CH3C1 40..- CHSCOOHZCOOCH -do.-- (O2H50)3P (CsH5O)= 1 -O C=G CHaOCHa142-145 0.01

CHgOCHa COOCH 3.1-. 91-94" 0. under 0.01 mm. Hg. 013100113 OH: H 47.CH3COCH2COO(C2H4O)0CH3 1113113100: (CHaOhP (CHaO)z%O J=C V ride. aCOO(C2H4O)9CH3 non-dlstillable, very readily soluble in water, acetoneand alcohol.

CH3 H 48... 0H3C0CH000 C2H4OMOH3 ---do..-.- (C2H50);P (CaH);i OC )=Oooowlmoncm non-dlstillable, very readily soluble in water, acetone andalcohol.

. 0115 01 49-.. CH:COCH2COO(C2H4O)9CH3 (CHBOMP (CB3O) i -O( 3='C x CO O(C2H4O)9CH3 non-distillable, solulole in water, acetone and alcohol.

CH; Cl 50-.. CH3COCH:COO(C2H40)9CH3 -do-. (C2H O)aP (C HiO)1 ?-OCC c 00ointment non-distillable, soluble in water, acetoneand alcohol.

A mixture of 22.45 parts of a-chloroacetoacet'ic acid-2- Example 7ethylmercapto ethyl ester (acetoacetic acid-Z-ethylmer- 'capto ethylester, boiling at 88 C. under 0.04 mm. Hg

pressure) and 25 parts by volume of chlorobenzene is heated to 140 C.This mixture is treated dropwise with 13.6 parts of trimethyl ph'osphiteand then stirredfor 1 hour at the boil, after which time 3.9 parts ofmethyl chloride have collected in a cooled receptacle.

The

readily volatile constituents are removed in vacuo at 90 C. bathtemperature, to yield as residue 26.4 parts of a pale-yellow vacuum. Thecompound boils at C. under 0.1 mm.

65 Hg pressure and corresponds to the formula Example 8 When 17.8 partsof a-chloroacetoacetic acid-Z-ethylmercapto ethyl ester are reacted with14.5 parts of triethyl 15 phosphite as described in Example 7, thecompound of the formula is obtained as a pale-yellow oil which issparingly soluble in water but readily soluble in acetone and propanol.

Example 9 When 25.9 parts of aza-dichloroacetoacetic acid-2-ethylmercapto ethyl ester are reacted with 13.6 parts of trimethylphosphite in 30 parts by volume of chlorobenzene as described in Example7, the compound of the formula ll omens-o C=O is obtained; it cannot bedistilled in a high vacuum and is sparingly soluble in water and readilysoluble in acetone and propanol.

Example 10 is obtained; it cannot be distilled in a high vacuum and isreadily soluble in acetone and propanol and sparingly soluble in water.

Example 11 12.62 parts of monochloroacetoacetic acid carbitol ester (seeTable No. 21) are mixed with 20 parts by volume of chlorobenzene andheated at 130 C. 9.65 parts of O-diethyl-N-diethylamidophosphite 2 5)2 zs)z are added dropwise. The reaction is completed by boiling the mixtureunder reflux for one hour, by which time 2.3 parts of ethyl chloridehave collected in a cooled receptacle. 'Ihe volatile constituents andthe solvent are removed in vacuo at 90 C., then in a high vacuum at 100C. bath temperature. The residue (17.2 parts) has the empirical formulaC H NO P and cannot be distilled in a high vacuum. The compound is lessthan 1% soluble in water but readily soluble in acetone and isopropanol.

Percent P found 8.3 P calculated -8..12n

Example 12 2.3 parts of sodium chips are added to 150 parts by volume ofdry ether; 21.8 parts of acetoacetic acid carbitol ester are addeddropwise to the mixture in the course of A of an hour. The mixture isheated at the boil until all the sodium has dissolved. 17.25 parts offreshly distilled diethylchlorophosphate (C H O) POCl are added dropwiseto this solution at 2030 C., and the whole is heated for 14 hours at theboil. 7 The mixture is allowed to cool and filtered ofi from theseparted sodium chloride (5.45 parts). The filtrate is washed with partsby volume of sodium carbonate solution, then with 10 parts by volume ofwater and then dried over sodium sulfate. After evaporating the solvent,there are obtained as residue 30.85 parts of the condensation product ofthe empirical formula C I-1 0 1 which boils at 143 C. in high vacuumunder 0,04 o pre ure.

- Percent P found 8.82 P calculated 8.74

Example 13 Percent P found 8.84 P calculated 8.36

Example 14 2.3 parts of sodium are added to 70 parts by volume ofabsolute ether. 13.8 parts of freshly distilled diethyl phosphite areadded dropwise at 20-30 C. The mixture is heated at the boil until allthe sodium has dissolved. 25.25 parts of monochloroacetoacetic acidcarbitol ester dissolved in 20 parts by volume of ether are addeddropwise at 20-30 C. in the course of half an hour. The reaction mixtureis then kept at boiling temperature for 16 hours. The ethereal solutionis washed with 10 parts by volume of sodium carbonate solution and twicewith 10 parts by volume of water each time, dried over sodium sulfateand evaporated under reduced pressure at 60 C. bath temperature. Theresidue (30.6 parts) is distilled in a high vacuum. Boiling point=160168C. under 0.05 mm. of pressure.

The phosphorus analysis of the condensation product obtained correspondsto the empirical formula C H O P.

' Percent P found P calculated Example 15 2 parts of the condensationproduct No. 3, 5, 9 or 17 in the table in Example 6 are mixed with 7parts of isopropanol and with 1 part of the condensation product from 1molecular proportion of tertiary octylphenol with 8 mols of ethyleneoxide. A clear solution is obtained which can be used as a sprayingpreparation concentrate and can be emulsifed by being poured into water.

To determine the contact efiect on aphids the following experiment wascarried out with sprays containing respectively 0.08%, 0.04%, 0.02% and0.01% of the active principle.

Broad beans, strongly infested with aphids, were sprayed 'all over andafter 48 hours the effect was determined.

When the spraying had produced a eifect, the plants were infected withfresh aphids and the effect again inspected after another 48 hours. Theresults achieved are listed in the following table:

For each plant a symbol is used: signifies that no living aphids werefound; signifies an insufficient or no effect; signifies good efiect,only few living aphids. p

7 (B) To determine the eliect on aphids by difiusion through the leavesthe following experiment was carried Efiect on aphids ComfzeutrationSpray No. 3 No. 5 No. 9 No. 17

(C) To determine the inner therapeutic (the so-called systemic) effectthe following experiment was carried out with sprays containingrespectively 0.08%, 0.04%, 0.02% and 0.01% of active principle.

From broad beans (Vicia fabae), strongly infested with aphids (Doralisfabae), the bottom leaves were removed and halfway up the stem a colourmark was made. The bottom half of the stem of two plants each was thensprayed with thepreparations of the under-mentioned concentrations.After 48 hours the efiects on aphids in the upper, unsprayed' half ofthe plants was inspected. The results obtained in this. manner are shownin the following table:

Eflect on aphids after 48 hours For each plant a symbol is used:signifies that no living aphids were found; signifies an insuflieient orno effect; signifies good effect, only few living aphids. In addition,compounds Nos. 3, 5, 9 and 17 displays a good acaricidal action againstred spiders (Tetranyehidae).

The spray preparation concentrates can alternatively be manufacturedwith wetting and emulsifying agents other than those mentioned above.For this purpose are suitable non-ionic products, for examplecondensation products of aliphatic alcohols, amines, or carboxylic acidswith a long-chain residue of about 10 to 30 carbon atoms with ethyleneoxide, such as the condensation product of octadecyl alcohol with 25 to30 mols of ethylene oxide; or the condensation product of soybean fattyacid with 30 mols of ethylene oxide; or of commercial octadecenylaminewith mols of ethylene oxide; or of dodecylmercaptan with 12 mols ofethylene oxide. Among suitable anion-active emulsifiers may :bementioned the sodium salt of dodecyl alcohol-sulfonic acid ester, thesodium salt of dodecylbenzenesulfonic acid, the potassium salt ortriethanolamine salt of oleic acid or of abietic acid or of mixtures ofthese acids, or the sodium salt of a petroleum-sulfonic acid.

Instead of isopropanol there may be used other solvents for themanufacture of the spray preparation concentrates, for example ethanol,methanol, butanol, acetone, methylethyl ketone, methyl-cyclohexanol,benzene, toluene, xylene, kerosenes or petroleum fractions, or mixturesof two or more solvents.

Example 16 2 parts of the condensation product No. 3, 5, 9', or 17 inthe table in Example 6 are mixtd with 9 parts of chalk and 1 part ofwetting agent. A dusting powder is obtained which can be suspended inwater to form a liquid spray. When the walls of stables are treated with18 such a spray containing 0.4% of active principle a good. effect onflies and midges is observed.

Example 17 In experiments carried out to-test'the effect on aphids bythe methods described in Example 15 under (a) and (b), the compounds ofExamples 110' and the compounds Nos. 1, 2, 4, 6-8,10-16, 18-41 and 43-48in the table in Example 6 likewise displayed good to excellent effects.

in tests for their aphidicidal" effect by the method described under (0)in Example 15,.the compounds referred to in Example 5 and the compoundsNos. 4, 6, 8, 10, 18, 21, 22, 28, 29, 32, 33, 36, 37, 40, 43 and 44 inthe table in Example 6 likewiseproduced a good to very good systemiceffect.

The compounds in Examples 5, 8, 9, 10 and the compounds Nos. 4, 6, 10,13, 14, 15, 16, 18, 21, 22, 28,. 29, 32, 33, 36, 37, 40, 41, 43, 44, 47and 48 in the table in Example 6 also displayed a good to outstandingacaricidal effect on red spiders.

What is claimed is: v

1. Organic phosphorus compounds of the formulain which each of R and Ris a member selected from the group consisting of lower alkyl,cyclohexyl, benzyl and phenyl radicals; R is a member selected from thegroup consisting of (a) an alkyl radical containing up to 19 carbonatoms which is interrupted by 2 to 9 ether oxygen atoms, (b) a radicalof the formula in which A and A represent lower alkylene radicals and nis a positive whole number of at most 2, and (c) a lower alkyl radicalinterrupted by a sulfur atom; R represents a member selected from thegroup consisting of a hydrogen atom, a chlorine atom and a lower alkylradical; R represents a member selected from the group consisting of alower alkyl, a cyclohexyl and a phenyl radical; each of X and Y is amember selected from the group consisting of O-- and interrupted by 2 to9 ether oxygen atoms, (b) a radical of the formula in which A and Arepresent lower alkylene radicals and n is a positive whole number of atmost 2, and (c) a lower alkyl radical interrupted by a sulfur atom; andR is a member selected from the group consisting of a hydrogen atom anda chlorine atom.

, 3. Organic phosphorus compounds of the general formula 4 in which R;is selected from the group consisting of a hydrogen atom and a chlorineatom, A is an alkyl radical containing 1 to 4 carbon atoms, 1: and xeach represent a whole number of at most 2 and y is a whole number from2 to 9, the whole group F 'l L J, containing at most 19 carbon atoms.

4. Organic phosphorus compounds of the general formula in which R isselected from the group consisting of a hydrogen atom and a chlorineatom, A and A each are an alkyl radical containing 1 to 4 carbon atomsand x and x each represent a Whole number of at most 2.

5. Organic phosphorus compounds of the general in which R, is selectedfrom the group consisting of a hydrogen atom and a chlorine atom and xand x each represent a whole number of at most 2.

O OH: H 10. The compound of the formula (oH=o)-IE0 :o-co 0CzH S-C;H

, 0 OH: H 11. The compound of the formula 01 (C2HBO)T ZEOC=C ReferencesCited in the file of this patent UNITED STATES PATENTS 2,685,552 StilesAug. 3, 1954 2,894,618 Lorenz July 7, 1959 2,982,686 Whetstone et al May2, 1961 OTHER REFERENCES Agricultural Chemicals, April 1953, pp. 47 to50, 137 and 139.

Journal Economic Entomology, April 1959, vol. 52, pp. 270 to 276. V

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,014,955 December 26, 1961 Ernst Beriger It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 2, line 47, for "bromide" read b rf omine columns 7 and 8, in thetable, column 4, line 7 thereof for "(CH 0) O" read (CH O) P columns 9and 10, in the table column 5, the formula opposite item 21 shouldappear as shown below instead of as in the patent:

0 CH3 H columns 11 and 12, in the table, columnf5, the formula oppositeitem 34 should appear as shown below instead of as in the patent:

0 CH c1 COOC H OCH(CH same columns 11 and 12, in the table, column 4,line 14 thereof for "(CH O) P" read'- (CH O) P column 16, line 7, for-"caribitol" read carbitol column 17, line 72, for "mixtd" read mixedcolumn 20, lines 18 to 20, the

formula should appear as shown below instead of as in the patent:

Signed and sealed this 11th day of September 1962.

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents

1. ORGANIC PHOSPHORUS COMPOUNDS OF THE FORMULA